Organic antimony compound, process for producing the same, living radical polymerization initiator, process for producing polymer using the same, and polymer

Abstract

An organoantimony compound represented by the formula (1), processes for producing polymers with use of the compound, and polymers wherein R 1 and R 2 are C 1 -C 8 alkyl, aryl, substituted aryl or an aromatic heterocyclic group, R 3 and R 4 are each a hydrogen atom or C 1 -C 8 alkyl, and R 5 is aryl, substituted aryl, an aromatic heterocyclic group, oxycarbonyl or cyano.

1. An organoantimony compound represented by the formula (1): 
       
         
           
           
               
               
           
         
         wherein R 1  and R 2  are C 1 -C 8  alkyl, aryl, substituted aryl, or an aromatic heterocyclic group; R 3  and R 4  are each a hydrogen atom or C 1 -C 8  alkyl; and R 5  is an aryl group unsubstituted or substituted by halogen, hydroxyl, alkoxyl, amino, nitro, cyano, —COR a  (wherein R a  is C 1 -C 8  alkyl, aryl, C 1 -C 8  alkoxyl, or aryloxyl), sulfonyl, or trifluoromethyl, an aromatic heterocyclic group, oxycarbonyl, or cyano; 
         provided that R 3  and R 4  are not hydrogen atoms simultaneously. 
       
     
     
       2. A process for preparing an organoantimony compound of the formula (1) of  claim 1  comprising reacting a compound of the formula (3): 
       
         
           
           
               
               
           
         
         (wherein R 1  and R 2  are as defined previously, and Z is a halogen atom or an alkali metal) 
         and a compound of the formula (4) or (5): 
       
       
         
           
           
               
               
           
         
         (wherein R 3 , R 4 , and R 5  are as defined previously, and X is a halogen atom) 
       
       
         
           
           
               
               
           
         
         (wherein R 3 , R 4 , and R 5  are as defined previously). 
       
     
     
       3. A living radical polymerization initiator represented by the formula (2): 
       
         
           
           
               
               
           
         
         wherein R 1  and R 2  are C 1 -C 8  alkyl, aryl, substituted aryl, or an aromatic heterocyclic group; R 3  and R 4  are each a hydrogen atom or C 1 -C 8  alkyl; and R 6  is an aryl group unsubstituted or substituted by halogen, hydroxyl, alkoxyl, amino, nitro, cyano, —COR a  (wherein R a  is C 1 -C 8  alkyl, aryl, C 1 -C 8  alkoxyl, or aryloxyl), sulfonyl, or trifluoromethyl, an aromatic heterocyclic group, oxycarbonyl, or cyano. 
       
     
     
       4. A process for producing a living radical polymer wherein a vinyl monomer is polymerized with use of a living radical polymerization initiator of the formula (2) of  claim 3 . 
     
     
       5. A process for producing a living radical polymer wherein a vinyl monomer is polymerized with use of a living radical polymerization initiator of the formula (2) of  claim 3  and an azo type polymerization initiator. 
     
     
       6. A mixture of a living radical polymerization initiator of the formula (2) of  claim 3  and an azo type polymerization initiator. 
     
     
       7. A process for producing a random copolymer wherein at least two vinyl monomers are polymerized with use of a living radical polymerization initiator of the formula (2) of  claim 3 . 
     
     
       8. A process for producing a random copolymer wherein at least two vinyl monomers are polymerized with use of a living radical polymerization initiator of the formula (2) of  claim 3  and an azo type polymerization initiator. 
     
     
       9. A macro living radical polymerization initiator which is obtainable by subjecting a vinyl monomer to polymerization with use of a living radical polymerization initiator of the formula (2) of  claim 3 . 
     
     
       10. A macro living radical polymerization initiator which is obtainable by subjecting a vinyl monomer to polymerization with use of a living radical polymerization initiator of the formula (2) of  claim 3  and an azo type polymerization initiator. 
     
     
       11. A process for producing a block copolymer wherein a vinyl monomer is polymerized with use of a macro living radical polymerization initiator of  claim 9 . 
     
     
       12. A process for producing a block copolymer wherein a vinyl monomer is polymerized with use of a macro living radical polymerization initiator of  claim 10 . 
     
     
       13. A process for producing a living radical polymer wherein a vinyl monomer is polymerized with use of a mixture of a living radical polymerization initiator of the formula (2) of  claim 3 , and at least one compound selected from a ditelluride compound, a distibine compound, and a dibismuthine compound. 
     
     
       14. A process for producing a living radical polymer wherein a vinyl monomer is polymerized with use of a mixture of a living radical polymerization initiator of the formula (2) of  claim 3 , an azo type polymerization initiator, and at least one compound selected from a ditelluride compound, a distibine compound, and a dibismuthine compound. 
     
     
       15. A living radical polymer which is obtainable by subjecting a vinyl monomer to polymerization with use of a mixture of a living radical polymerization initiator of the formula (2) of  claim 3 , and at least one compound selected from a ditelluride compound, a distibine compound, and a dibismuthine compound. 
     
     
       16. A living radical polymer which is obtainable by subjecting a vinyl monomer to polymerization with use of a mixture of a living radical polymerization initiator of the formula (2) of  claim 3 , an azo type polymerization initiator, and at least one compound selected from a ditelluride compound, a distibine compound, and a dibismuthine compound. 
     
     
       17. A mixture of a living radical polymerization initiator of the formula (2) of  claim 3 , and at least one compound selected from a ditelluride compound, a distibine compound, and a dibismuthine compound. 
     
     
       18. A mixture of a living radical polymerization initiator of the formula (2) of  claim 3 , an azo type polymerization initiator, and at least one compound selected from a ditelluride compound, a distibine compound, and a dibismuthine compound. 
     
     
       19. A process for producing a random copolymer wherein at least two vinyl monomers are polymerized with use of a mixture of a living radical polymerization initiator of the formula (2) of  claim 3 , and at least one compound selected from a ditelluride compound, a distibine compound, and a dibismuthine compound. 
     
     
       20. A process for producing a random copolymer wherein at least two vinyl monomers are polymerized with use of a mixture of a living radical polymerization initiator of the formula (2) of  claim 3 , an azo type polymerization initiator, and at least one compound selected from a ditelluride compound, a distibine compound, and a dibismuthine compound. 
     
     
       21. A macro living radical polymerization initiator which is obtainable by subjecting a vinyl monomer to polymerization with use of a mixture of a living radical polymerization initiator of the formula (2) of  claim 3 , and at least one compound selected from a ditelluride compound, a distibine compound, and a dibismuthine compound. 
     
     
       22. A macro living radical polymerization initiator which is obtainable by subjecting a vinyl monomer to polymerization with use of a mixture of a living radical polymerization initiator of the formula (2) of  claim 3 , an azo type polymerization initiator, and at least one compound selected from ditelluride compound, a distibine compound, and a dibismuthine compound. 
     
     
       23. A process for producing a block copolymer wherein a vinyl monomer is polymerized with use of the macro living radical polymerization initiator of  claim 21 . 
     
     
       24. A process for producing a block copolymer wherein a vinyl monomer is polymerized with use of the macro living radical polymerization initiator of  claim 22 . 
     
     
       25. A process for producing a resin containing an acid-dissociable group wherein a vinyl monomer is polymerized with use of one of the following (a) to (d):
 (a) a living radical polymerization initiator of the formula (2) of  claim 3 ; 
 (b) a mixture of a living radical polymerization initiator of the formula (2), and an azo type polymerization initiator; 
 (c) a mixture of a living radical polymerization initiator of the formula (2), and at least one compound selected from a ditelluride compound, a distibine compound, and a dibismuthine compound; and 
 (d) a mixture of a living radical polymerization initiator of the formula (2), an azo type polymerization initiator, and at least one compound selected from a ditelluride compound, a distibine compound, and a dibismuthine compound.